The eldest son of King Ferdinand II of the Two Sicilies and his second wife Archduchess Maria Theresa of Austria, he was heir presumptive to his elder half-brother King Francis II of the Two Sicilies from 1859 to 1861.

Prince Louis was born on 1 August 1838 in Naples as the second son of Ferdinand II, King of the Two Sicilies, and his second wife Maria Theresa of Austria, a daughter of Archduke Charles of Austria, Duke of Teschen.

Their father died on 22 May 1859, and Luigi's older brother ascended the throne of the Two Sicilies as King Francis II.

As Francis still had no children from his wife Maria Sophie of Bavaria, Prince Louis became his heir presumptive.

Francis was eventually succeeded by their younger brother Prince Alfonso, Count of Caserta.